Design of self-cleaning TiO2 coating on clay roofing tiles

The phenomenon of heterogeneous photocatalysis takes place in the degradation process of many organic contaminants on solid surfaces. Photocatalysis is based on the excitation of the semiconductor by irradiation with supraband gap photons and the migration of electron-hole pairs to the surface of the photocatalysts, leading to the reaction of the holes with adsorbed H₂O and OH^? to form hydroxyl radicals. Due to the stability and photosensitivity of TiO₂ semiconductors, this system is well studied and is of great interest from an ecological and industrial point of view for use in the field of building materials. Clay roofing tiles, due to their long-term exploitation, are subject to physical, chemical and biological degradation that leads to deterioration. Ceramic systems have a high percentage of total porosity and considering their non-tolerance of organic coating, the use of surface active materials (SAM) that induce porosity in TiO₂ coatings is of vital significance. Photocatalytic coatings applied on clay roofing tiles under industrial conditions were designed by varying the quantity of TiO₂ (mass/cm²) on the tile surface (thin and thick TiO₂ layer). The positive changes in specific surface area and mesopore structure of the designed coatings were made by the addition of PEG 600 as a surface active material. It was shown that a thin photocatalytic layer (0.399 mg suspension/cm² tile surface), applied onto ceramic tiles under industrial conditions, had better photocatalytic activity in methylene blue decomposition, hydrophilicity and antimicrobial activity than a thick photocatalytic coating (0.885 mg suspension/cm²).     

Comparison of Inductively Coupled Plasma with Classical Analytical Techniques in the Analysis of Southern Oregon Lithia Water: Inclusion of a Local Resource in the Undergraduate Chemistry Curriculum

Abstract

Lithia water, a community resource of local historical significance, is described as a central theme in the undergraduate analytical chemistry sequence. A statistical comparison of the classical determination of major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and anions (HCO₃ ^?, Cl^?) reinforces statistical and charge‐balance concepts covered in analytical chemistry. Subsequent determination of these major cations by inductively coupled plasma (ICP) enables students to statistically evaluate the presence of bias between instrumental and classical methods. The effect of easily ionized elements on ICP calibration sensitivity and linearity via the use of cesium as an ionization suppressor is reported.     

The quadruplex-duplex structural transition of polyriboguanylic acid

The vibrational infrared (IR) absorption and vibrational circular dichroism (VCD) spectral changes of polyriboguanylic acid (polyG) as a function of time, temperature and pH have been investigated to establish how changes in spectral features relate to the structural modifications of polyG. From the progression of IR and VCD spectral features with respect to time, it is observed that stabilization of the quadruplex structure at pH 6.4 (near-neutral environment) takes place within 5 days. This stabilization process is most clearly evidenced by a downshift of the carbonyl absorption band and the corresponding positive VCD couplet, from 1689 to approximately 1682 cm(-1) in time. Time-induced spectral modifications also indicated that, in an acidic environment (pH 3.1) and within a 5 day waiting period, polyG develops a duplex structure. An additional positive VCD couplet associated with an absorption band at 1589 cm(-1) is identified as a marker of the polyG duplex structure. From the progression of spectral features with respect to temperature at pH 6.4, it is found that heating induces structural changes that favor the formation of a duplex structure. This duplex structure, at pH 6.4, would not form at room temperature simply by the passage of time. When polyG is in an acidic environment (pH 3.1), heating accelerates the conversion to the duplex structure that could also be obtained with passage of time at that pH. On the basis of the comparison of experimental and quantum theoretical VCD spectra for polyG, the key spectral signature for the quadruplex form is considered to be a single positive VCD couplet, while the spectral signature for a duplex form is considered to contain an additional positive VCD couplet at a lower frequency.     

Chiroptical spectroscopic determination of molecular structures of chiral sulfinamides: t-butanesulfinamide

The absolute configuration of t-butanesulfinamide has been determined as (-)-(S) using three different chiroptical spectroscopic methods, namely, vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD). Furthermore, the predominant conformation of this molecule is determined to have S=O and NH2 groups staggered with respect to the three methyl groups and to have amine hydrogens in gauche orientation with respect to S=O. The quality of predictions obtained for vibrational properties, namely, vibrational absorption and VCD, is found to be satisfactory with the B3LYP functional and 6-31G* basis set. However, this basis set is found to be inadequate for obtaining reliable predictions of electronic properties, namely, electronic absorption and ECD, but a larger aug-cc-pVDZ basis set is found to provide satisfactory prediction of electronic properties. t-Butanesulfinamide serves as an example which invalidates the recommendation of using the 6-31G* basis set for molecules that exhibit the same sign for the long-wavelength ECD band and ORD. This molecule also emphasizes the importance of simultaneous investigation of ECD and ORD, and the use of multiple chiroptical spectroscopic methods, for reliable determination of molecular stereochemistry.     

Synthesis and reactivity of copper(I) complexes containing a bis(imidazolin-2-imine) pincer ligand

The new pincer ligand 2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine (TL(tBu)) has been prepared in high yield from 2,6-bis(hydroxymethyl)pyridine (1) and 1,3-di-tert-butylimidazolin-2-imine (3). Reaction of TL(tBu) with [Cu(MeCN)4]PF6 affords the highly reactive copper(I) complex [(TL(tBu))Cu]PF6, [5]PF6, which forms the stable copper(I) isocyanide complexes [6a]PF6 (nu(CN) = 2179 cm(-1)) and [6b]PF6 (nu(CN) = 2140 cm(-1)) upon addition of tert-butyl or 2,6-dimethylphenyl isocyanide, respectively. For the cations 6a and 6b, DFT calculations reveal ground-state electronic structures of the type [(TL(tBu)-kappaN(1):kappaN(2))Cu(CNR)] with tricoordinate geometries around the copper atoms. Exposure of [5]PF6 to the air readily leads to trapping of atmospheric CO2 to form the square-planar complex [(TL(tBu))Cu(HCO3-kappaO)]PF6, [7]PF6, with the bicarbonate ligand adopting a rarely observed monodentate coordination mode. In chlorinated solvents such as dichloromethane or chloroform, [5]PF(6) rapidly abstracts chloride by reductive dechlorination of the solvent to yield [(TL(tBu))CuCl]PF6, [8]PF6 quantitatively. Reaction of TL(tBu) with copper(I) bromide or chloride affords complexes 9a and 9b, respectively, for which X-ray diffraction analysis, low-temperature NMR experiments and DFT calculations reveal the presence of a kappa(2)-coordinated ligand of the type [(TL(tBu)-kappaN(1):kappaN(2))CuX]. In solution, complex 9b undergoes slow disproportionation forming the mixed-valence copper(II)/copper(I) system [(TL(tBu))CuCl][CuCl2], [8]CuCl2 with a linear dichlorocuprate(I) counterion.     

Gas phase activation energy for unimolecular dissociation of biomolecular ions determined by focused RAdiation for gaseous multiphoton ENergy transfer (FRAGMENT)

We present a novel approach for the determination of activation energy for the unimolecular dissociation of a large (>50 atoms) ion, based on measurement of the unimolecular dissociation rate constant as a function of continuous-wave CO(2) laser intensity. Following a short ( approximately 1 s) induction period, CO(2) laser irradiation produces an essentially blackbody internal energy distribution, whose 'temperature' varies inversely with laser intensity. The only currently available method for measuring such activation energies is blackbody infrared radiative dissociation (BIRD). Compared with BIRD, FRAGMENT: (a) eliminates the need to heat the surrounding ion trap and vacuum chamber to each of several temperatures (each requiring hours for temperature equilibration); (b) offers a three-fold wider range of effective blackbody temperature; and (c) extends the range of applications to include initially cold ions (e.g., gas-phase H/D exchange). Our FRAGMENT-determined activation energy for dissociation of protonated bradykinin, 1.2 +/- 0.1 eV, agrees within experimental error to the value, 1.3 +/- 0.1 eV, previously reported by Williams et al. from BIRD experiments. Copyright 1999 John Wiley & Sons, Ltd.     

Total synthesis and structural elucidation of azaspiracid-1. Synthesis-based analysis of originally proposed structures and indication of their non-identity to the natural product

The key building blocks (6, 7, and 8) for the intended construction of the originally proposed structures of azaspiracid-1, a potent marine-derived neurotoxin, were coupled and the products elaborated to the targeted compounds (1a,b) and their C-20 epimers (2 and 3). The assembly of the three intermediates was accomplished by a dithiane-based coupling reaction that united the C(1)-C(20) (7) and C(21)-C(27) (8) fragments, followed by a Stille-type coupling which allowed the incorporation of the C(28)-C(40) fragment (6) into the growing substrate. Neither of the final products (1a,b) matched the natural substance by TLC or (1)H NMR spectroscopic analysis, suggesting one or more errors in the originally proposed structure for this notorious biotoxin.     

Thermal destruction of spin-polaron bands in the narrow-gap correlated semiconductors FeGa3 and FeSb2

We report muon spin rotation spectra in the narrow-gap semiconductors FeGa(3) and FeSb(2) consistent with a narrow band of small spin polarons (SPs). The characteristic sizes obtained for these SPs are R(FeGa(3)) ≈ 0.3-0.6 nm and R(FeSb (2)) ≈ 0.3 nm, respectively. Such SP states are expected to originate from the exchange correlations between localized and itinerant electrons. Our data suggest that SP bands are formed at low temperature, but are destroyed by thermal fluctuations above 10 K in FeGa(3) and above 7 K in FeSb(2). Formation of such SP band states can explain many of the low-temperature properties of these materials.